CA2134490C - Process for the preparation of a high purity cobalt intermediate - Google Patents
Process for the preparation of a high purity cobalt intermediate Download PDFInfo
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- CA2134490C CA2134490C CA002134490A CA2134490A CA2134490C CA 2134490 C CA2134490 C CA 2134490C CA 002134490 A CA002134490 A CA 002134490A CA 2134490 A CA2134490 A CA 2134490A CA 2134490 C CA2134490 C CA 2134490C
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0476—Separation of nickel from cobalt
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
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Abstract
A process for the preparation and purification of a cobalt intermediate from a cobalt sulphate solution containing cationic and anionic impurities, including the successive steps of:
(i) reacting the cobalt sulphate solution with an organic reagent to extract unwanted cationic impurities from the sulphate solution;
(ii) extracting the cobalt from the sulphate solution with an organic reagent, to create a cobalt loaded organic phase substantially free of all anionic impurities;
(iii) stripping the cobalt loaded organic phase with a high strength ammoniacal ammonium carbonate solution, to create an ammoniacal ammonium carbonate strip liquor rich in cobalt II ammines;
(iv) converting the cobalt II ammines to cobalt III tetrammines;
(v) extracting the majority of nickel from the cobalt rich ammoniacal liquor with a suitable organic reagent; and (vi) recovering the cobalt from the cobalt rich ammoniacal liquor.
(i) reacting the cobalt sulphate solution with an organic reagent to extract unwanted cationic impurities from the sulphate solution;
(ii) extracting the cobalt from the sulphate solution with an organic reagent, to create a cobalt loaded organic phase substantially free of all anionic impurities;
(iii) stripping the cobalt loaded organic phase with a high strength ammoniacal ammonium carbonate solution, to create an ammoniacal ammonium carbonate strip liquor rich in cobalt II ammines;
(iv) converting the cobalt II ammines to cobalt III tetrammines;
(v) extracting the majority of nickel from the cobalt rich ammoniacal liquor with a suitable organic reagent; and (vi) recovering the cobalt from the cobalt rich ammoniacal liquor.
Description
-'- ~ ~34~9 0 PROCESS FOR THE PREPARATION OF A HIGH PURITY
COBALT INTERMEDIATE
The present invention resides in a process for the preparation of a high purity s cobalt intermediate substantially free of both cationic and anionic impurities. The process allows for a cobalt intermediate to be recovered in high yield and purity from an ammoniacal ammonium carbonate solution of the cobalt tetrammine complex.
In prior art processes nickel and cobalt bearing ores and concentrates may for io example be processed by the reduction roast .ammonium carbonate oxidative leach route. By this route, impure cobalt sulphide is produced as a by-product, and the isolation and recovery of this by-product is illustrated in Australian Patent 605867.
The recovery of cobalt as a sulphide is achieved by injection of a suitable is sulphiding agent, for example, gaseous hydrogen sulphide or ammonium hydrosulphide solution. This procedure however results in the precipitation of sulphides of other elements present such as iron, zinc, copper and nickel as well as the adsorption and or coprecipitation of compounds that normally do not produce insoluble sulphides, such as calcium, magnesium and manganese.
In order to produce pure cobalt metal or a pure cobalt compound for industrial applications it is necessary to first solubilize the impure sulphides and then isolate the cobalt in a suitable form free of unwanted impurities.
2s A number of processes have been reported describing the isolation of cobalt as a pure product. These procedures usually involve a combination of solubilization, precipitation, solvent extraction and electrowinning operations. One such process, known as the Nippon Mining Corporation process, recovers cobalt in the metallic form by electrowinning from an acidic sulphate solution. Another process, known as the 3o Sumitomo process, also recovers cobalt in mei:allic form however this is electrowon from a chloride solution. Both of these operations have common features in that the cobalt is present in the cobaltous state at the point of isolation and the product is a massive metal cathode plate:
3s Another commercial cobalt sulphide rei~ining process is the soluble cobaltic ammine process developed by Sherritt Gordon Mines Ltd. This process involves solubilization, precipitation of hydrated ferric oxide, conversion of the cobaltous sulphate to cobaltic pentammine sulphate, precipitation of nickel ammonium sulphate, reduction of the cobaltic pentammine to cobaltous diammine and, finally, pressure 4o hydrogen reduction to cobalt metal powder.
Cobalt has many applications and not all of these require cobalt metal. For example, cobalt salts find use in a variety of industries and significant quantities of cobalt oxide are also used industrially. Consequently, a pure cobalt compound able to be converted to salts, oxides and fine metal powder would be a useful industrial commodity.
s The present invention aims to overcome or at least alleviate one or more of the difficulties associated with the prior art.
The present development relates to a suitable method of purifying cobalt by a io combination of solubilization, solvent extraction and optionally ion exchange operations that allows cobalt to be recovered from a solution in which it is present in the cobaltic state.
The present invention resides in a process for the preparation of a cobalt is intermediate substantially free of both cationic .and anionic impurities from impure cobalt sulphide, wherein the process is characterised by solvent extraction in both an acidic medium and basic ammoniacal medium to remove both cationic and anionic impurities.
In particular, in a first aspect, the present invention resides in a process for the 2o preparation and purification of a cobalt oxide hydroxide compound from a cobalt sulphate solution containing cationic and anionic impurities comprising the successive steps of:
(i) contacting the cobalt sulphate solution with an organic reagent for the 2s extraction of ferric iron and zinc at an initial pH of less than 2.8 to extract the majority of ferric iron cationic impurities from the cobalt sulphate solution and slowly raising the pH to about 3.5 to separate the remaining iron and zinc cationic impurities from the cobalt sulphate solution;
30 (ii) extracting the cobalt from the sulphate solution with another organic reagent to produce a cobalt loaded organic phase substantially free of all anionic impurities;
(iii) stripping the cobalt loaded organic phase with a concentrated ammoniacal ammonium carbonate solution to produce an ammoniacal ammonium carbonate strip liquor rich in cobalt II ammines;
s (iv) oxidising the cobalt II ammines in the ammoniacal ammonium carbonate strip liquor to cobalt III tetraammines to form a cobalt III tetraammine rich ammoniacal liquor;
(v) extracting the majority of nickel, as an impurity from the cobalt III
tetraammine rich io ammoniacal liquor with an organic reagent; and (vi) recovering the cobalt from the cobalt III tetraammine rich ammoniacal ammonium carbonate strip liquor.
";, _,. Q~3449 p Most profarably the process also indudes a furd~er extrac~iowstep wherein further unwanted cationic impurities are removed by contacting the oobak rich ammoniscal liquor with an ion exchange resin.
s The invention is d~araced in that the process sequentisNll treats a cobalt u~g solution to nsmowe impurities such as iron, zinc" copper. manganese, nickel, magnesium and calci~nn and empbys an scidlbase solvent extraction transfer step to romove anionic impurities such as sulphate, d~loride and nkrate. The pnefemed i o fiestures of the ~vention wiN become evident from the to~owirrg din.
The process of the irwention is parkadwly applicable to recovering cobak firom insoluble cobalt sulphide soNds. The methods ava~able to cornrort irwohrble oobak sulphide solids to solubb oobek sales aro varied and they genereNy require the injection is of a~ or oxygen at atrnospheric or higher pressure into an aqueous shiny of the solids at ebvabed ternperafiuro. Fa the purposes of this solub~Zation std, it is protem~ fio inject ar or oxygen at a bornpereture range of 60°C to 90°C at ast~mmospheric pressure, the reaction period can be adjusted to achieve the degros of solution requ'N~ed.
The temperaturo may be controlled by the circulaakeon of water or steam. The end n3suk 2o is the production of a sohrdon of oobak su~habs of pH IoHVer than 2.5 wkh cobak concentration of 30 to 90 gl-~~ pnefie~l~l bout 50-65 g~'.
During the dissolution of the cobalt sulphide, the impurity elements present also dissowe. This ahoars the ootmlt solution to be subjected to the appropriate Pub 2s steps. The Nippon Mining Corporation. Sumibomo and Sheriff Gordar processes each employ ~ procipitetion step to remove iron as tertic hydroxide from the cobak sulphate solution. Ha~wevsr, when fierric hydroxide prec~itates from cobsk-rich aqueous solutions; some cobak is lost, adsorbed to. a ooprecipitatsd with the ferric hydroxide solids. This ropresents a oobak loss that is not easily reversed. Most preferably, the 3o present invention employs an organic reagent a nrogents speafic for ferric iron and zinc at predetermined pH values to strip any iron and zinc from the sohrtion wkhout any signif~au~t loss of cobalt, which avoids the ditfiarky of the prior art processes.
k is particularly profemed that the organic reagent for the extraction of cationic 3s impurities tom the cobalt sulphate solution is speafic for the extraction of ferric iron and zinc. It is most desirable that the iron present in the oobak sulphate solution be ferric (Fe3+) ions, and accordingly the cobak sulphate sohrtion may be treated with a strong oxidant, for example hydrogen peroodda, to comrert any iron present to ferric iron.
-"~ 213449 ~
It should be appreciated that control of pH during solvent extraction is important if complete and selective separations are to~ be achieved. For the process of the present invention, it is most desired to maintain the pH value of the solution initially s between a pH value of less than 2.8, preferably from about 2.1 to 2.6, which will generally separate about 95% of the ferric iron from the solution, and slowly raising the pH to about 3.5 specific for zinc separation. The present invention enables ferric iron and zinc to be selectively and effectively removed in sequence from the acidic cobalt sulphate solution.
io A suitable organic reagent for this step has been found to be a phosphinic acid derivative dissolved in a kerosene solvent, for example a preferred reagent is bis(2,4,4,trimethylpentyl)phosphinic acid in aliphatic kerosene (Escaid 110).
The ratios of these components may be adjusted to yield the required optimum extraction and is stripping properties.
The effectiveness of the removal for iron and zinc from aqueous cobalt sulphate solution utilizing the above procedure is illustrated by the results in Table 1.
Co/Fe ratio Co/Zn ratio Cobalt Sulphate feed Liquor 100 30 2s Treated Liquor 40,000 150,000 Loaded Strip Liquor 0.0005 0.0001 Consideration of the nature of the desired high purity cobalt intermediate requires that not only cationic but also anionic impurities need to be removed. It has been found 3o that this may be achieved if the cobalt is transferred from an acidic sulphate medium to a basic ammoniacal ammonium carbonate medium.
In order to transfer the cobalt from the acidic sulphate solution, the cobalt may be extracted with a suitable organic reagent to create a cobalt loaded organic phase.
3s Those familiar with solvent extraction chemistry will appreciate that only cations will chemically transfer to the organic reagent, while anions will remain with the aqueous phase. Consequently there has been a separation of cobalt from anionic impurities such as sulphate, chloride and nitrate ions.
-s-~13449 0 Most suitably the organic reagent is a phosphoric acid derivative dissolved in kerosene and modified with an aliphatic long chain alcohol. A preferred organic reagent to effect the transfer of cobalt from an acid medium to an ammoniacal ammonium carbonate medium was found to be a mixture of di(2-ethylexyl)phosphoric s acid, iso-tridecanol and aliphatic kerosene in suitable proportions to yield optimum extraction and stripping properties.
The reaction generally takes place in mixer settler extraction cells. Some cationic impurities may also transfer to the organic phase.
io The cobalt loaded organic reagent exiting the extraction cells may also physically remove some aqueous phase containing sulphate and in order to remove this contamination the cobalt loaded organic reagE:nt may be transferred to mixer settler scrub cells. An aqueous scrub liquor which may be either dilute ammonia, dilute is ammonium carbonate or deionized water is used to contact the organic phase to remove entrained aqueous sulphate, chloride and nitrate impurities.
The cobalt loaded organic phase exiting the scrub cells is transferred to mixer settler strip cells where the cobalt is stripped from the organic phase by high strength 2o ammoniacal ammonium carbonate solution. A solution of composition 205 to 330g1-' ammonium and 160 to 300 gl-' carbon dioxide, preferably 255 to 300 gl-' ammonia and 200 to 260 gl-' carbon dioxide, and most preferably 285 gl-1 ammonia and 230 gl-1 carbon dioxide has been found most effective. It should be understood that by varying the ratio of strip liquor to cobalt loaded organic phase, considerable increases in cobalt 2s concentration in the aqueous strip phase can be achieved. The nature of the cobalt rich ammoniacal liquor is illustrated by the data in Table 2.
3o Co ;S04 2-Cobalt Sulphate Feed Liquor 50 gl-1 100 gl-1 Loaded Ammoniacal Liquor 80 gl-1 5 ppm 3s Nickel may now be removed from the ammoniacal liquor. The separation of nickel from cobalt in ammoniacal carbonate liquors is influenced greatly by two factors:-(i) the presence of cobalt (II) ammiines, and (ii) the ammonia concentration of the cobalt rich liquor.
In order to effectively remove nickel from the cobalt rich ammoniacal liquor produced by the cationic transfer process outlined above, the labile cobalt II
ammines s should be converted to stable cobalt III tetrarnmine. This is generally achieved by sparging the cobalt rich ammoniacal liquor with air or oxygen and hydrogen peroxide in order to oxidise the cobalt II to cobalt III. During this oxidation step, the cobalt II
ammine concentration is generally lowered frorn about 20 gl-1 to about 50 ppm.
The cobalt III tetrammine rich ammoniacal liquor may be subjected to controlled distillation io to lower the uncomplexed NH3 concentration to approximately 20-60 gl-', preferably about 40 gl-1 without destabilizing the cobalt ammine and causing precipitation of solids in the distillation column. Cooling of this ammoniacal liquor is preferred to control its temperature prior to transfer to a series of solvent extraction cells to effect nickel removal.
Is In order to effectively lower the nickel concentration of the cobalt tetrammine rich ammoniacal liquor to a suitably low value, it is preferred to use an organic reagent with very low residual nickel loading. This is a natural consequence of the equilibrium relationship between an element in an organic and aqueous phase in contact.
The most preferred organic reagent used in this step is either an oxime reagent, for example, an acetophenoneoxime or salicylaldoxime, or a substituted beta diketone, in kerosene and modified by the addition of a long chain aliphatic alcohol, for example iso-tridecanol, iso-undecanol, iso-dodecanol, and the corresponding linear type. The 2s preferred reagent is a mixture of 2-hydroxy-5-t-nonyl acetophenoneoxime in aliphatic kerosene modified by the addition of iso-tridecanol. This reagent stream may be contacted with high strength ammoniacal amnnonium carbonate liquor, with a typical concentration of from 205 to 33081-' ammonia, preferably 280 gl-', and 160 to 300 gl-' carbon dioxide preferably 230 gl-' to remove nickel from the organic reagent.
This 3o reaction generally takes place in a series of mixer settler cells at a strip cell temperature of between 35° to 55°C for a period of betweE:n 30 seconds and 30 minutes in each cell, preferably 3 minutes.
The nickel free organic reagent may then contact the cobalt III tetrammine rich 3s ammoniacal liquor to remove the nickel impuri~~ty from the cobalt liquor..
This reaction may be carried out in mixer settlers and the u;>ual factors of organic to aqueous ratio, temperature, residence time in the mixer boxes and numbers of strip and extract cells should be optimized. For example, a suitable organic to aqueous ratio may be 0.2:1 to 5:1, preferably 1:1 to 2:1, at a temperature in the extract cells of between 35°C and 40 60°C, for a period of between 30 seconds and 30 minutes, preferably about 3 minutes.
-'- 213449 0 The effectiveness of this circuit is illustrated by the data presented in Table 3.
s Co Ni Ammoniacal Feed Liquor 60 gl-1 1.8 gl-1 Treated Liquor 60 gl-1 1 ppm io Copper and manganese which are usually present at levels of up to 20 ppm in the ammoniacal feed liquor are also extracted to residual levels of less than 2 ppm during this extraction.
The cobalt tetrammine rich ammoniacal liquor essentially free of nickel, iron, zinc, is copper, manganese, sulphate and chloride ions may then be subjected to filtration through an activated carbon bed (to scavenge any entrained organic reagent removed from the nickel extraction circuit) before being contacted with a suitably conditioned ion exchange resin in order to remove any residual calcium and magnesium.
2o A number of ion exchange resins were tested, however given the nature of the feed solution and the duty required from the ion exchange resin the most preferred is a chelating ion exchange resin of the Iminodiacetate type with a high affinity for calcium and magnesium. Given the nature of the feed solution, cobalt tetrammine rich with calcium and magnesium in ammoniacal ammonium carbonate, it is most preferred that 2s the resin be conditioned prior to use to avoid the evolution of gas and disruption of the resin bed during operation. It will be appreciated that during ion exchange resin operations, gas evolution may have a detrimental effect on the operating efficiency of an ion exchange system.
3o For continuous operation three individual ion exchange resin columns are most preferred, two operating in series with the third on standby following regeneration. This enables control of the calcium and magnesium impurities associated with cobalt exiting the ion exchange resin system. The effectiveness of this system is illustrated by the data in Table 4.
3s Co Mg Ca Ammoniacal Feed Liquor 60 gl-1 200 ppm 50 ppm ao Treated Liquor 60 gl-1 1 ppm 1 ppm The cobalt rich ammoniacal liquor exiting the ion exchange resin system contains extremely low levels of both cationic and anionic impurities. The cobalt III
tetrammine complex while stable at ambient temperatures is readily destroyed at elevated s temperatures forming an insoluble cobaltic .oxide hydroxide virtually free of any contaminating anions such as sulphate, chloride and nitrate.
In order to recover the cobalt in an intermediate form, in one preferred way, the cobalt tetrammine rich ammoniacal liquor may be delivered continuously under io controlled conditions to a multi-tray distillation column heated with steam. The off gases are condensed and recovered while the aqueous slurry is pumped to a thickener to recover the suspended cobaltic oxide hydroxide solids.
These solids because of their composition, particle size and purity are an ideal is intermediate from which to prepare a range of cobalt end products.
Typical composition of the cobaltic oxide hydroxide solids produced is given in Table 5.
Typical Value Typical Value %.
Co 64 Mg 0.001 Ni 0.001 Ca 0.001 2s Fe 0.001 AI 0.001 Cu 0.001 Si 0.001 Zn 0.001 Na 0.001 Mn 0.001 CI <0.001 so As an alternative step, the cobalt liquor exiting the ion exchange resin system may also be treated in a reductive step by contacting the liquor with finely divided pure cobalt metal powder to reduce the cobalt III tetrammine to labile cobalt II
ammine.
This reaction may take place in an inert ;atmosphere at from 25°C to 35°C and results in the precipitation of cobalt hydroxy carbonate solids. The solution is distilled to 3s recover ammonia and carbon dioxide while driving the precipitation reaction to completion.
According to a second aspect, the preaent invention also resides in cobalt intermediate compounds, produced by the procEas of the present invention as outlined 4o above.
_ -9- 213449 0 By way of example, figure 1 provides a flow diagram of the process according to the present invention. It will be appreciated tlhat this chart is merely illustrative of a preferred embodiment of the invention, and the invention should not be considered s limited thereto.
The process flow diagram (Fig 1) for the present invention illustrates the injection of air (1) into four reactor units (A), (B), (C) and (D) and the injection of oxygen (2) into two reactor units (E) and (F) at atmospheric pressure. The reaction temperature can be io controlled at the required value, 60° to 90°C by the circulation of water or steam through appropriately positioned coiled tube. The reaction period can be adjusted to achieve the degree of solubilization of cobalt sulphide solids to soluble cobalt salts required, the liquor leaving the final reaction unit (F) is a solution of cobalt sulphate of pH less than 2.5 units and cobalt concentration varying from 30 to 90 gl-' and which is is passed through a filter (G) to remove any particulate matter.
For the extraction of cationic impurities, iron and zinc, it is most desired that the iron present in stream (3) exiting filter (G) be treated with a strong oxidant, for example hydrogen peroxide stream (4), to ensure only ferric (Fe3+) ions are present prior to 2o entering the first mixer settler extraction cell (H).
It is also most desired that the oxidised stream (5) during its progress through the mixer settler cells (H) and (I) is maintained at a ~>H of less than 2.8 units to eliminate the potential for the precipitation of ferric hydroxide within the solvent extraction circuit. For 2s the extraction of zinc also present in stream (5) 'to go to completion, a pH of 3.5 units is most desired, and therefore a basic reagent injection system (6) is required to maintain all the extraction cells (H), (I), (J) and (K) at the optimum pH to remove in the first case ferric iron and then to remove zinc.
3o The additional mixer settler cells illustrated in Fig. 1 are required to first remove any entrained cobalt rich aqueous phase from the iron and zinc loaded organic reagent stream (8). Cells (L) and (M) are used for this purpose, the scrub stream (9) used for this purpose may be water. The cobalt free iron and zinc loaded organic reagent (10) exiting scrub cell (M) is then subjected to stripping with dilute sulphuric acid (11) in ss mixer settler units (N), (O), (P) and (Q) before exiting mixer settler cell (Q) as stream (12) stripped organic reagent. This reagent stream again being available to extract iron and zinc on a continuous basis. Stream (13) is .a waste stream containing iron and zinc sulphate.
.~. -1~- 2~t3449 0 The cobalt sulphate solution stream (7) essentially free of iron and zinc contaminants, is pumped to mixer settler cell (R) where it is contacted with a suitable volume of an organic reagent mixture, for example, a mixture of di(2-ethylhexyl)phosphoric acid, iso-tridecanol and aliphatic kerosene, effecting a transfer of s cobalt from the aqueous phase to the organic phase.
Three mixer settler extraction cells (R), (S) and (T) were found adequate to maximise the cobalt extraction and the stream (14) leaving cell (T) is essentially cobalt free. The cobalt loaded organic reagent exitinc,~ extraction cell (R) stream (15) may be io contaminated with physically associated aqueous liquor containing anionic impurities.
Since the object of the above transfer step is to separate cobalt from anionic impurities, it is most preferred to pump the cobalt loadedl organic reagent to mixer settler scrub cells where the organic phase is contacted with deionized water (16) to remove impurities. Two scrub cells (U) and (~ are used and the scrub stream containing some is cobalt (20) is returned to extraction cell (R) for recovery.
The scrubbed cobalt loaded organic reagent (17) exiting scrub cell (~ enters mixer settler strip cell (1/~ where it contacts ammoniacal ammonium carbonate strip liquor leaving strip cell (X). This countercurrent progression of organic and aqueous 2o phases continues through the four strip cells (\,~, (llln, (X) and (Y) required to recover the cobalt from the organic reagent. The most suitable liquor for the above described cobalt stripping procedure was found to be one containing 285 gl-' of ammonia and 230 gl-' of carbon dioxide.
2s The ammoniacal ammonium carbonate ;>trip liquor stream (18), free of cobalt, enters strip cell (Z) and exits strip cell (llln, stream (19) containing approximately 80 gl-' cobalt. The cobalt rich liquor stream (19) is plumped to two reactor vessels in series (A1 ) and (A2) and air and or oxygen (21 ) injecte:d during vigorous agitation of the liquor to convert cobalt II ammines to cobalt III ammine~s.
The oxidised liquor exiting vessel (A2) is agitated in vessel (A3) during the injection of hydrogen peroxide (22) to complete the oxidation cycle. The oxidised liquor (23) will have been depleted in ammonia to some extent as the injection of air will remove free ammonia, the extent of removal depending on the reaction time. The 3s oxidised liquor (23) rich in cobalt III ammines may now be subjected to controlled distillation in column (A4) to lower the unc:omplexed ammonia concentration to approximately 40 gl-' without destabilizing the cobalt ammines and causing precipitation in the distillation column. Steam (24) is injected into the column to effect the removal of ammonia. Stream (25) is an off gas stream containing NH3, C02 and steam and is ao condensed for recycling.
In order to effectively lower the nickel concentration of the cobalt tetrammine rich ammoniacal liquor exiting the distillation column, stream (26), to a suitably low value, it is preferred to use an organic reagent with very low residual nickel loading.
This is a s natural consequence of the equilibrium relationship between an element in an organic and aqueous phase in contact.
The most preferred organic reagent used iin this step is a mixture of 2-hydroxy-5-t-nonyl acetophenoneoxime in aliphatic kerosene modified by the addition of iso-io tridecanol. This reagent stream (27) enters mixer settler strip cells (A8), (A9) and (A10) where it is contacted with high strength ammoniacal ammonium carbonate liquor (28), typical composition 280 gl-' ammonia and 230 gl-' carbon dioxide, to remove nickel from the organic reagent. The nickel free organic reagent stream (29) now contacts the cobalt tetrammine rich ammoniacal liquor (26) in a series of 3 extract mixer settler units is (A5), (A6) and (A7) to remove the nickel impurity from the cobalt liquor. A
suitable organic to aqueous phase ratio may be 1:1 at an extract cell temperature of between 35° and 60°C and a strip cell temperature of between 35°
and 55°C for a period of between 30 seconds and 30 minutes.
2o The cobalt tetrammine rich ammoniacal liquor (30) is then passed through two ion exchange columns in series (A11) and (A12) to lower calcium and magnesium impurities to acceptable levels.
In order to recover the cobalt as an ini:ermediate, the cobalt tetrammine rich 2s ammoniacal ammonium carbonate liquor (31 ) is delivered continuously under controlled conditions to a multi tray distillation column (A13'~) and heated with steam.
The aqueous slurry (32) is pumped to a thickener (A14) to recover the suspended cobaltic oxide hydroxide solids prior to filtration through filter (A,15) to produce a moist filter cake.
so It will also be appreciated, that various modifications or alterations may be made to the invention as outlined above, without dep<~rting from the spirit or ambit described therein, and should be considered to form part of the invention.
COBALT INTERMEDIATE
The present invention resides in a process for the preparation of a high purity s cobalt intermediate substantially free of both cationic and anionic impurities. The process allows for a cobalt intermediate to be recovered in high yield and purity from an ammoniacal ammonium carbonate solution of the cobalt tetrammine complex.
In prior art processes nickel and cobalt bearing ores and concentrates may for io example be processed by the reduction roast .ammonium carbonate oxidative leach route. By this route, impure cobalt sulphide is produced as a by-product, and the isolation and recovery of this by-product is illustrated in Australian Patent 605867.
The recovery of cobalt as a sulphide is achieved by injection of a suitable is sulphiding agent, for example, gaseous hydrogen sulphide or ammonium hydrosulphide solution. This procedure however results in the precipitation of sulphides of other elements present such as iron, zinc, copper and nickel as well as the adsorption and or coprecipitation of compounds that normally do not produce insoluble sulphides, such as calcium, magnesium and manganese.
In order to produce pure cobalt metal or a pure cobalt compound for industrial applications it is necessary to first solubilize the impure sulphides and then isolate the cobalt in a suitable form free of unwanted impurities.
2s A number of processes have been reported describing the isolation of cobalt as a pure product. These procedures usually involve a combination of solubilization, precipitation, solvent extraction and electrowinning operations. One such process, known as the Nippon Mining Corporation process, recovers cobalt in the metallic form by electrowinning from an acidic sulphate solution. Another process, known as the 3o Sumitomo process, also recovers cobalt in mei:allic form however this is electrowon from a chloride solution. Both of these operations have common features in that the cobalt is present in the cobaltous state at the point of isolation and the product is a massive metal cathode plate:
3s Another commercial cobalt sulphide rei~ining process is the soluble cobaltic ammine process developed by Sherritt Gordon Mines Ltd. This process involves solubilization, precipitation of hydrated ferric oxide, conversion of the cobaltous sulphate to cobaltic pentammine sulphate, precipitation of nickel ammonium sulphate, reduction of the cobaltic pentammine to cobaltous diammine and, finally, pressure 4o hydrogen reduction to cobalt metal powder.
Cobalt has many applications and not all of these require cobalt metal. For example, cobalt salts find use in a variety of industries and significant quantities of cobalt oxide are also used industrially. Consequently, a pure cobalt compound able to be converted to salts, oxides and fine metal powder would be a useful industrial commodity.
s The present invention aims to overcome or at least alleviate one or more of the difficulties associated with the prior art.
The present development relates to a suitable method of purifying cobalt by a io combination of solubilization, solvent extraction and optionally ion exchange operations that allows cobalt to be recovered from a solution in which it is present in the cobaltic state.
The present invention resides in a process for the preparation of a cobalt is intermediate substantially free of both cationic .and anionic impurities from impure cobalt sulphide, wherein the process is characterised by solvent extraction in both an acidic medium and basic ammoniacal medium to remove both cationic and anionic impurities.
In particular, in a first aspect, the present invention resides in a process for the 2o preparation and purification of a cobalt oxide hydroxide compound from a cobalt sulphate solution containing cationic and anionic impurities comprising the successive steps of:
(i) contacting the cobalt sulphate solution with an organic reagent for the 2s extraction of ferric iron and zinc at an initial pH of less than 2.8 to extract the majority of ferric iron cationic impurities from the cobalt sulphate solution and slowly raising the pH to about 3.5 to separate the remaining iron and zinc cationic impurities from the cobalt sulphate solution;
30 (ii) extracting the cobalt from the sulphate solution with another organic reagent to produce a cobalt loaded organic phase substantially free of all anionic impurities;
(iii) stripping the cobalt loaded organic phase with a concentrated ammoniacal ammonium carbonate solution to produce an ammoniacal ammonium carbonate strip liquor rich in cobalt II ammines;
s (iv) oxidising the cobalt II ammines in the ammoniacal ammonium carbonate strip liquor to cobalt III tetraammines to form a cobalt III tetraammine rich ammoniacal liquor;
(v) extracting the majority of nickel, as an impurity from the cobalt III
tetraammine rich io ammoniacal liquor with an organic reagent; and (vi) recovering the cobalt from the cobalt III tetraammine rich ammoniacal ammonium carbonate strip liquor.
";, _,. Q~3449 p Most profarably the process also indudes a furd~er extrac~iowstep wherein further unwanted cationic impurities are removed by contacting the oobak rich ammoniscal liquor with an ion exchange resin.
s The invention is d~araced in that the process sequentisNll treats a cobalt u~g solution to nsmowe impurities such as iron, zinc" copper. manganese, nickel, magnesium and calci~nn and empbys an scidlbase solvent extraction transfer step to romove anionic impurities such as sulphate, d~loride and nkrate. The pnefemed i o fiestures of the ~vention wiN become evident from the to~owirrg din.
The process of the irwention is parkadwly applicable to recovering cobak firom insoluble cobalt sulphide soNds. The methods ava~able to cornrort irwohrble oobak sulphide solids to solubb oobek sales aro varied and they genereNy require the injection is of a~ or oxygen at atrnospheric or higher pressure into an aqueous shiny of the solids at ebvabed ternperafiuro. Fa the purposes of this solub~Zation std, it is protem~ fio inject ar or oxygen at a bornpereture range of 60°C to 90°C at ast~mmospheric pressure, the reaction period can be adjusted to achieve the degros of solution requ'N~ed.
The temperaturo may be controlled by the circulaakeon of water or steam. The end n3suk 2o is the production of a sohrdon of oobak su~habs of pH IoHVer than 2.5 wkh cobak concentration of 30 to 90 gl-~~ pnefie~l~l bout 50-65 g~'.
During the dissolution of the cobalt sulphide, the impurity elements present also dissowe. This ahoars the ootmlt solution to be subjected to the appropriate Pub 2s steps. The Nippon Mining Corporation. Sumibomo and Sheriff Gordar processes each employ ~ procipitetion step to remove iron as tertic hydroxide from the cobak sulphate solution. Ha~wevsr, when fierric hydroxide prec~itates from cobsk-rich aqueous solutions; some cobak is lost, adsorbed to. a ooprecipitatsd with the ferric hydroxide solids. This ropresents a oobak loss that is not easily reversed. Most preferably, the 3o present invention employs an organic reagent a nrogents speafic for ferric iron and zinc at predetermined pH values to strip any iron and zinc from the sohrtion wkhout any signif~au~t loss of cobalt, which avoids the ditfiarky of the prior art processes.
k is particularly profemed that the organic reagent for the extraction of cationic 3s impurities tom the cobalt sulphate solution is speafic for the extraction of ferric iron and zinc. It is most desirable that the iron present in the oobak sulphate solution be ferric (Fe3+) ions, and accordingly the cobak sulphate sohrtion may be treated with a strong oxidant, for example hydrogen peroodda, to comrert any iron present to ferric iron.
-"~ 213449 ~
It should be appreciated that control of pH during solvent extraction is important if complete and selective separations are to~ be achieved. For the process of the present invention, it is most desired to maintain the pH value of the solution initially s between a pH value of less than 2.8, preferably from about 2.1 to 2.6, which will generally separate about 95% of the ferric iron from the solution, and slowly raising the pH to about 3.5 specific for zinc separation. The present invention enables ferric iron and zinc to be selectively and effectively removed in sequence from the acidic cobalt sulphate solution.
io A suitable organic reagent for this step has been found to be a phosphinic acid derivative dissolved in a kerosene solvent, for example a preferred reagent is bis(2,4,4,trimethylpentyl)phosphinic acid in aliphatic kerosene (Escaid 110).
The ratios of these components may be adjusted to yield the required optimum extraction and is stripping properties.
The effectiveness of the removal for iron and zinc from aqueous cobalt sulphate solution utilizing the above procedure is illustrated by the results in Table 1.
Co/Fe ratio Co/Zn ratio Cobalt Sulphate feed Liquor 100 30 2s Treated Liquor 40,000 150,000 Loaded Strip Liquor 0.0005 0.0001 Consideration of the nature of the desired high purity cobalt intermediate requires that not only cationic but also anionic impurities need to be removed. It has been found 3o that this may be achieved if the cobalt is transferred from an acidic sulphate medium to a basic ammoniacal ammonium carbonate medium.
In order to transfer the cobalt from the acidic sulphate solution, the cobalt may be extracted with a suitable organic reagent to create a cobalt loaded organic phase.
3s Those familiar with solvent extraction chemistry will appreciate that only cations will chemically transfer to the organic reagent, while anions will remain with the aqueous phase. Consequently there has been a separation of cobalt from anionic impurities such as sulphate, chloride and nitrate ions.
-s-~13449 0 Most suitably the organic reagent is a phosphoric acid derivative dissolved in kerosene and modified with an aliphatic long chain alcohol. A preferred organic reagent to effect the transfer of cobalt from an acid medium to an ammoniacal ammonium carbonate medium was found to be a mixture of di(2-ethylexyl)phosphoric s acid, iso-tridecanol and aliphatic kerosene in suitable proportions to yield optimum extraction and stripping properties.
The reaction generally takes place in mixer settler extraction cells. Some cationic impurities may also transfer to the organic phase.
io The cobalt loaded organic reagent exiting the extraction cells may also physically remove some aqueous phase containing sulphate and in order to remove this contamination the cobalt loaded organic reagE:nt may be transferred to mixer settler scrub cells. An aqueous scrub liquor which may be either dilute ammonia, dilute is ammonium carbonate or deionized water is used to contact the organic phase to remove entrained aqueous sulphate, chloride and nitrate impurities.
The cobalt loaded organic phase exiting the scrub cells is transferred to mixer settler strip cells where the cobalt is stripped from the organic phase by high strength 2o ammoniacal ammonium carbonate solution. A solution of composition 205 to 330g1-' ammonium and 160 to 300 gl-' carbon dioxide, preferably 255 to 300 gl-' ammonia and 200 to 260 gl-' carbon dioxide, and most preferably 285 gl-1 ammonia and 230 gl-1 carbon dioxide has been found most effective. It should be understood that by varying the ratio of strip liquor to cobalt loaded organic phase, considerable increases in cobalt 2s concentration in the aqueous strip phase can be achieved. The nature of the cobalt rich ammoniacal liquor is illustrated by the data in Table 2.
3o Co ;S04 2-Cobalt Sulphate Feed Liquor 50 gl-1 100 gl-1 Loaded Ammoniacal Liquor 80 gl-1 5 ppm 3s Nickel may now be removed from the ammoniacal liquor. The separation of nickel from cobalt in ammoniacal carbonate liquors is influenced greatly by two factors:-(i) the presence of cobalt (II) ammiines, and (ii) the ammonia concentration of the cobalt rich liquor.
In order to effectively remove nickel from the cobalt rich ammoniacal liquor produced by the cationic transfer process outlined above, the labile cobalt II
ammines s should be converted to stable cobalt III tetrarnmine. This is generally achieved by sparging the cobalt rich ammoniacal liquor with air or oxygen and hydrogen peroxide in order to oxidise the cobalt II to cobalt III. During this oxidation step, the cobalt II
ammine concentration is generally lowered frorn about 20 gl-1 to about 50 ppm.
The cobalt III tetrammine rich ammoniacal liquor may be subjected to controlled distillation io to lower the uncomplexed NH3 concentration to approximately 20-60 gl-', preferably about 40 gl-1 without destabilizing the cobalt ammine and causing precipitation of solids in the distillation column. Cooling of this ammoniacal liquor is preferred to control its temperature prior to transfer to a series of solvent extraction cells to effect nickel removal.
Is In order to effectively lower the nickel concentration of the cobalt tetrammine rich ammoniacal liquor to a suitably low value, it is preferred to use an organic reagent with very low residual nickel loading. This is a natural consequence of the equilibrium relationship between an element in an organic and aqueous phase in contact.
The most preferred organic reagent used in this step is either an oxime reagent, for example, an acetophenoneoxime or salicylaldoxime, or a substituted beta diketone, in kerosene and modified by the addition of a long chain aliphatic alcohol, for example iso-tridecanol, iso-undecanol, iso-dodecanol, and the corresponding linear type. The 2s preferred reagent is a mixture of 2-hydroxy-5-t-nonyl acetophenoneoxime in aliphatic kerosene modified by the addition of iso-tridecanol. This reagent stream may be contacted with high strength ammoniacal amnnonium carbonate liquor, with a typical concentration of from 205 to 33081-' ammonia, preferably 280 gl-', and 160 to 300 gl-' carbon dioxide preferably 230 gl-' to remove nickel from the organic reagent.
This 3o reaction generally takes place in a series of mixer settler cells at a strip cell temperature of between 35° to 55°C for a period of betweE:n 30 seconds and 30 minutes in each cell, preferably 3 minutes.
The nickel free organic reagent may then contact the cobalt III tetrammine rich 3s ammoniacal liquor to remove the nickel impuri~~ty from the cobalt liquor..
This reaction may be carried out in mixer settlers and the u;>ual factors of organic to aqueous ratio, temperature, residence time in the mixer boxes and numbers of strip and extract cells should be optimized. For example, a suitable organic to aqueous ratio may be 0.2:1 to 5:1, preferably 1:1 to 2:1, at a temperature in the extract cells of between 35°C and 40 60°C, for a period of between 30 seconds and 30 minutes, preferably about 3 minutes.
-'- 213449 0 The effectiveness of this circuit is illustrated by the data presented in Table 3.
s Co Ni Ammoniacal Feed Liquor 60 gl-1 1.8 gl-1 Treated Liquor 60 gl-1 1 ppm io Copper and manganese which are usually present at levels of up to 20 ppm in the ammoniacal feed liquor are also extracted to residual levels of less than 2 ppm during this extraction.
The cobalt tetrammine rich ammoniacal liquor essentially free of nickel, iron, zinc, is copper, manganese, sulphate and chloride ions may then be subjected to filtration through an activated carbon bed (to scavenge any entrained organic reagent removed from the nickel extraction circuit) before being contacted with a suitably conditioned ion exchange resin in order to remove any residual calcium and magnesium.
2o A number of ion exchange resins were tested, however given the nature of the feed solution and the duty required from the ion exchange resin the most preferred is a chelating ion exchange resin of the Iminodiacetate type with a high affinity for calcium and magnesium. Given the nature of the feed solution, cobalt tetrammine rich with calcium and magnesium in ammoniacal ammonium carbonate, it is most preferred that 2s the resin be conditioned prior to use to avoid the evolution of gas and disruption of the resin bed during operation. It will be appreciated that during ion exchange resin operations, gas evolution may have a detrimental effect on the operating efficiency of an ion exchange system.
3o For continuous operation three individual ion exchange resin columns are most preferred, two operating in series with the third on standby following regeneration. This enables control of the calcium and magnesium impurities associated with cobalt exiting the ion exchange resin system. The effectiveness of this system is illustrated by the data in Table 4.
3s Co Mg Ca Ammoniacal Feed Liquor 60 gl-1 200 ppm 50 ppm ao Treated Liquor 60 gl-1 1 ppm 1 ppm The cobalt rich ammoniacal liquor exiting the ion exchange resin system contains extremely low levels of both cationic and anionic impurities. The cobalt III
tetrammine complex while stable at ambient temperatures is readily destroyed at elevated s temperatures forming an insoluble cobaltic .oxide hydroxide virtually free of any contaminating anions such as sulphate, chloride and nitrate.
In order to recover the cobalt in an intermediate form, in one preferred way, the cobalt tetrammine rich ammoniacal liquor may be delivered continuously under io controlled conditions to a multi-tray distillation column heated with steam. The off gases are condensed and recovered while the aqueous slurry is pumped to a thickener to recover the suspended cobaltic oxide hydroxide solids.
These solids because of their composition, particle size and purity are an ideal is intermediate from which to prepare a range of cobalt end products.
Typical composition of the cobaltic oxide hydroxide solids produced is given in Table 5.
Typical Value Typical Value %.
Co 64 Mg 0.001 Ni 0.001 Ca 0.001 2s Fe 0.001 AI 0.001 Cu 0.001 Si 0.001 Zn 0.001 Na 0.001 Mn 0.001 CI <0.001 so As an alternative step, the cobalt liquor exiting the ion exchange resin system may also be treated in a reductive step by contacting the liquor with finely divided pure cobalt metal powder to reduce the cobalt III tetrammine to labile cobalt II
ammine.
This reaction may take place in an inert ;atmosphere at from 25°C to 35°C and results in the precipitation of cobalt hydroxy carbonate solids. The solution is distilled to 3s recover ammonia and carbon dioxide while driving the precipitation reaction to completion.
According to a second aspect, the preaent invention also resides in cobalt intermediate compounds, produced by the procEas of the present invention as outlined 4o above.
_ -9- 213449 0 By way of example, figure 1 provides a flow diagram of the process according to the present invention. It will be appreciated tlhat this chart is merely illustrative of a preferred embodiment of the invention, and the invention should not be considered s limited thereto.
The process flow diagram (Fig 1) for the present invention illustrates the injection of air (1) into four reactor units (A), (B), (C) and (D) and the injection of oxygen (2) into two reactor units (E) and (F) at atmospheric pressure. The reaction temperature can be io controlled at the required value, 60° to 90°C by the circulation of water or steam through appropriately positioned coiled tube. The reaction period can be adjusted to achieve the degree of solubilization of cobalt sulphide solids to soluble cobalt salts required, the liquor leaving the final reaction unit (F) is a solution of cobalt sulphate of pH less than 2.5 units and cobalt concentration varying from 30 to 90 gl-' and which is is passed through a filter (G) to remove any particulate matter.
For the extraction of cationic impurities, iron and zinc, it is most desired that the iron present in stream (3) exiting filter (G) be treated with a strong oxidant, for example hydrogen peroxide stream (4), to ensure only ferric (Fe3+) ions are present prior to 2o entering the first mixer settler extraction cell (H).
It is also most desired that the oxidised stream (5) during its progress through the mixer settler cells (H) and (I) is maintained at a ~>H of less than 2.8 units to eliminate the potential for the precipitation of ferric hydroxide within the solvent extraction circuit. For 2s the extraction of zinc also present in stream (5) 'to go to completion, a pH of 3.5 units is most desired, and therefore a basic reagent injection system (6) is required to maintain all the extraction cells (H), (I), (J) and (K) at the optimum pH to remove in the first case ferric iron and then to remove zinc.
3o The additional mixer settler cells illustrated in Fig. 1 are required to first remove any entrained cobalt rich aqueous phase from the iron and zinc loaded organic reagent stream (8). Cells (L) and (M) are used for this purpose, the scrub stream (9) used for this purpose may be water. The cobalt free iron and zinc loaded organic reagent (10) exiting scrub cell (M) is then subjected to stripping with dilute sulphuric acid (11) in ss mixer settler units (N), (O), (P) and (Q) before exiting mixer settler cell (Q) as stream (12) stripped organic reagent. This reagent stream again being available to extract iron and zinc on a continuous basis. Stream (13) is .a waste stream containing iron and zinc sulphate.
.~. -1~- 2~t3449 0 The cobalt sulphate solution stream (7) essentially free of iron and zinc contaminants, is pumped to mixer settler cell (R) where it is contacted with a suitable volume of an organic reagent mixture, for example, a mixture of di(2-ethylhexyl)phosphoric acid, iso-tridecanol and aliphatic kerosene, effecting a transfer of s cobalt from the aqueous phase to the organic phase.
Three mixer settler extraction cells (R), (S) and (T) were found adequate to maximise the cobalt extraction and the stream (14) leaving cell (T) is essentially cobalt free. The cobalt loaded organic reagent exitinc,~ extraction cell (R) stream (15) may be io contaminated with physically associated aqueous liquor containing anionic impurities.
Since the object of the above transfer step is to separate cobalt from anionic impurities, it is most preferred to pump the cobalt loadedl organic reagent to mixer settler scrub cells where the organic phase is contacted with deionized water (16) to remove impurities. Two scrub cells (U) and (~ are used and the scrub stream containing some is cobalt (20) is returned to extraction cell (R) for recovery.
The scrubbed cobalt loaded organic reagent (17) exiting scrub cell (~ enters mixer settler strip cell (1/~ where it contacts ammoniacal ammonium carbonate strip liquor leaving strip cell (X). This countercurrent progression of organic and aqueous 2o phases continues through the four strip cells (\,~, (llln, (X) and (Y) required to recover the cobalt from the organic reagent. The most suitable liquor for the above described cobalt stripping procedure was found to be one containing 285 gl-' of ammonia and 230 gl-' of carbon dioxide.
2s The ammoniacal ammonium carbonate ;>trip liquor stream (18), free of cobalt, enters strip cell (Z) and exits strip cell (llln, stream (19) containing approximately 80 gl-' cobalt. The cobalt rich liquor stream (19) is plumped to two reactor vessels in series (A1 ) and (A2) and air and or oxygen (21 ) injecte:d during vigorous agitation of the liquor to convert cobalt II ammines to cobalt III ammine~s.
The oxidised liquor exiting vessel (A2) is agitated in vessel (A3) during the injection of hydrogen peroxide (22) to complete the oxidation cycle. The oxidised liquor (23) will have been depleted in ammonia to some extent as the injection of air will remove free ammonia, the extent of removal depending on the reaction time. The 3s oxidised liquor (23) rich in cobalt III ammines may now be subjected to controlled distillation in column (A4) to lower the unc:omplexed ammonia concentration to approximately 40 gl-' without destabilizing the cobalt ammines and causing precipitation in the distillation column. Steam (24) is injected into the column to effect the removal of ammonia. Stream (25) is an off gas stream containing NH3, C02 and steam and is ao condensed for recycling.
In order to effectively lower the nickel concentration of the cobalt tetrammine rich ammoniacal liquor exiting the distillation column, stream (26), to a suitably low value, it is preferred to use an organic reagent with very low residual nickel loading.
This is a s natural consequence of the equilibrium relationship between an element in an organic and aqueous phase in contact.
The most preferred organic reagent used iin this step is a mixture of 2-hydroxy-5-t-nonyl acetophenoneoxime in aliphatic kerosene modified by the addition of iso-io tridecanol. This reagent stream (27) enters mixer settler strip cells (A8), (A9) and (A10) where it is contacted with high strength ammoniacal ammonium carbonate liquor (28), typical composition 280 gl-' ammonia and 230 gl-' carbon dioxide, to remove nickel from the organic reagent. The nickel free organic reagent stream (29) now contacts the cobalt tetrammine rich ammoniacal liquor (26) in a series of 3 extract mixer settler units is (A5), (A6) and (A7) to remove the nickel impurity from the cobalt liquor. A
suitable organic to aqueous phase ratio may be 1:1 at an extract cell temperature of between 35° and 60°C and a strip cell temperature of between 35°
and 55°C for a period of between 30 seconds and 30 minutes.
2o The cobalt tetrammine rich ammoniacal liquor (30) is then passed through two ion exchange columns in series (A11) and (A12) to lower calcium and magnesium impurities to acceptable levels.
In order to recover the cobalt as an ini:ermediate, the cobalt tetrammine rich 2s ammoniacal ammonium carbonate liquor (31 ) is delivered continuously under controlled conditions to a multi tray distillation column (A13'~) and heated with steam.
The aqueous slurry (32) is pumped to a thickener (A14) to recover the suspended cobaltic oxide hydroxide solids prior to filtration through filter (A,15) to produce a moist filter cake.
so It will also be appreciated, that various modifications or alterations may be made to the invention as outlined above, without dep<~rting from the spirit or ambit described therein, and should be considered to form part of the invention.
Claims (2)
1. A process for the preparation and purification of a cobalt oxide hydroxide compound from a cobalt sulphate solution containing cationic and anionic impurities comprising the successive steps of:
(i) contacting the cobalt sulphate solution with an organic reagent for the extraction of ferric iron and zinc at an initial pH of less than 2.8 to extract the majority of ferric iron cationic impurities from the cobalt sulphate solution and slowly raising tree pH to about 3.5 to separate the remaining iron and zinc cationic impurities from the cobalt sulphate solution;
(ii) extracting the cobalt from the sulphate solution with another organic reagent to produce a cobalt loaded organic phase substantially free of all anionic impurities;
(iii) stripping the cobalt loaded organic phase with a concentrated ammoniacal ammonium carbonate solution to produce an ammoniacal ammonium carbonate strip liquor rich in cobalt II ammines;
(iv) oxidising the cobalt II ammines in the ammoniacal ammonium carbonate strip liquor to cobal III tetraammines to form a cobalt III
tetraammine richammoniacal liquor;
(v) extracting the majority of nickel, as an impurity from the cobalt III
tetraammine richammoniacal liquor with an organic reagent; and (vi) recovering the cobalt from the cobalt III tetraammine rich ammoniacal ammonium carbonate strip liquor.
1. A process according to Claim 1, wherein calcium and magnesium cationic impurities are extracted prior to the recovery step by contacting the cobalt III
tetraammine rich ammoniacal liquor with an ion exchange resin.
3. A process according to Claim 1, wherein impure cobalt sulphide solids are solubilized prior to step (i) to form the cobalt sulphate solution.
4. A process according to Claim 1, wherein the cobalt sulphate solution has pH
of less than 2.5 and a cobalt concentration of from 30 to 90 gl-1.
5. A process according to Claim 1, wherein the cobalt sulphate solution is treated with a strong oxidant to convert any iron impurities to ferric (Fe3+) ions prior to treating with the organic reagent of step (i).
6. A process according to Claim 1, wherein the organic reagent referred to in step (I) is a phosphinic acid derivative dissolved in a kerosene solvent and is specific for the extraction of ferric iron and zinc from the cobalt sulphate solution under controlled pH
conditions.
7. A process according to claim 6, wherein the organic reagent is bis(2,4,4-trimethylpentyl)phosphinic add in aliphatic kerosene.
8. A process according to claim 6, wherein the pH of the solution for step (i) is maintained at an initial pH of from 2.1 to 2.8 to separate approximately 95%
of the ferric iron from the cobalt sulphate solution.
9. A process according to claim 1, wherein the organic reagent used in step (ii) is a phosphoric acid derivative dissolved in kerosene and modified with an aliphatic long chain alcohol.
10. A process according to claim 9, wherein the organic reagent is a mixture of di(2-ethylhexyl) phosphoric acid, iso-tridecanol and aliphatic kerosene.
11. A process according to claim 1, wherein substantially all the anionic impurities remain in the sulphate solution following step (ii), and the cobalt loaded organic phase is subjected to an aqueous scrub liquor to remove any residual anionic impurities that may have physically transferred to the organic phase.
12. A process according to claim 1, wherein the cobalt is stripped from the cobalt loaded organic phase in step (iii) by a high strength ammoniacal ammonium carbonate solution having an ammonium content of from 205 to 330 gl-1 and a carbon dioxide content of from 180 to 300 gl-1.
13. A process according to claim 12, wherein the ammonium content is from 255 to 300 gl-1 and the carbon dioxide content is from 200 to 260 gl-1.
14. A process according to claim 13, wherein the ammonium content is about 285 gl-1 and the carbon dioxide content is about 230 gl-1.
15. A process according to claim 1, wherein prior to extracting the nickel from the ammoniacal ammonium carbonate strip liquor, the concentration of cobalt II
ammine in the strip liquor is lowered from about 20 gl-1 to 50ppm by sparging the strip liquor with air, oxygen or hydrogen peroxide;
and the concentration of the uncomplexed ammonium is lowered by controlled distillation to about 20-60 gl-1.
16. A process according to claim 1, wherein the organic reagent of step (v) is an oxime reagent in kerosene and modified by the addition of a long chap aliphatic alcohol.
17. A process according to claim 18, wherein the organic reagent is selected from
(i) contacting the cobalt sulphate solution with an organic reagent for the extraction of ferric iron and zinc at an initial pH of less than 2.8 to extract the majority of ferric iron cationic impurities from the cobalt sulphate solution and slowly raising tree pH to about 3.5 to separate the remaining iron and zinc cationic impurities from the cobalt sulphate solution;
(ii) extracting the cobalt from the sulphate solution with another organic reagent to produce a cobalt loaded organic phase substantially free of all anionic impurities;
(iii) stripping the cobalt loaded organic phase with a concentrated ammoniacal ammonium carbonate solution to produce an ammoniacal ammonium carbonate strip liquor rich in cobalt II ammines;
(iv) oxidising the cobalt II ammines in the ammoniacal ammonium carbonate strip liquor to cobal III tetraammines to form a cobalt III
tetraammine richammoniacal liquor;
(v) extracting the majority of nickel, as an impurity from the cobalt III
tetraammine richammoniacal liquor with an organic reagent; and (vi) recovering the cobalt from the cobalt III tetraammine rich ammoniacal ammonium carbonate strip liquor.
1. A process according to Claim 1, wherein calcium and magnesium cationic impurities are extracted prior to the recovery step by contacting the cobalt III
tetraammine rich ammoniacal liquor with an ion exchange resin.
3. A process according to Claim 1, wherein impure cobalt sulphide solids are solubilized prior to step (i) to form the cobalt sulphate solution.
4. A process according to Claim 1, wherein the cobalt sulphate solution has pH
of less than 2.5 and a cobalt concentration of from 30 to 90 gl-1.
5. A process according to Claim 1, wherein the cobalt sulphate solution is treated with a strong oxidant to convert any iron impurities to ferric (Fe3+) ions prior to treating with the organic reagent of step (i).
6. A process according to Claim 1, wherein the organic reagent referred to in step (I) is a phosphinic acid derivative dissolved in a kerosene solvent and is specific for the extraction of ferric iron and zinc from the cobalt sulphate solution under controlled pH
conditions.
7. A process according to claim 6, wherein the organic reagent is bis(2,4,4-trimethylpentyl)phosphinic add in aliphatic kerosene.
8. A process according to claim 6, wherein the pH of the solution for step (i) is maintained at an initial pH of from 2.1 to 2.8 to separate approximately 95%
of the ferric iron from the cobalt sulphate solution.
9. A process according to claim 1, wherein the organic reagent used in step (ii) is a phosphoric acid derivative dissolved in kerosene and modified with an aliphatic long chain alcohol.
10. A process according to claim 9, wherein the organic reagent is a mixture of di(2-ethylhexyl) phosphoric acid, iso-tridecanol and aliphatic kerosene.
11. A process according to claim 1, wherein substantially all the anionic impurities remain in the sulphate solution following step (ii), and the cobalt loaded organic phase is subjected to an aqueous scrub liquor to remove any residual anionic impurities that may have physically transferred to the organic phase.
12. A process according to claim 1, wherein the cobalt is stripped from the cobalt loaded organic phase in step (iii) by a high strength ammoniacal ammonium carbonate solution having an ammonium content of from 205 to 330 gl-1 and a carbon dioxide content of from 180 to 300 gl-1.
13. A process according to claim 12, wherein the ammonium content is from 255 to 300 gl-1 and the carbon dioxide content is from 200 to 260 gl-1.
14. A process according to claim 13, wherein the ammonium content is about 285 gl-1 and the carbon dioxide content is about 230 gl-1.
15. A process according to claim 1, wherein prior to extracting the nickel from the ammoniacal ammonium carbonate strip liquor, the concentration of cobalt II
ammine in the strip liquor is lowered from about 20 gl-1 to 50ppm by sparging the strip liquor with air, oxygen or hydrogen peroxide;
and the concentration of the uncomplexed ammonium is lowered by controlled distillation to about 20-60 gl-1.
16. A process according to claim 1, wherein the organic reagent of step (v) is an oxime reagent in kerosene and modified by the addition of a long chap aliphatic alcohol.
17. A process according to claim 18, wherein the organic reagent is selected from
2-hydroxy-5-t-nonyl acetophenoneoxime, 2-hydroxy-5-nonyl salicylaldoxime, alkyl, aryl and halide substituted beta diketones in an aliphatic or aromatic kerosene carrier, modified by an alcohol selected from iso-tridecanol, iso-undecanol, iso-dodecanol and the corresponding unbranched isomers.
18. A process according to claim 17, wherein the organic reagent is a mixture of 2-hydroxy-5-t-nonyl acetophenoneoxime in aliphatic kerosene, modified by the addition of iso-tridecanol.
19. A process according to claim 18, wherein prior to extracting nickel from the cobalt tetrammine rich ammoniacal liquor, any residual nickel is removed from the organic reagent by contacting the organic reagent with a high strength ammoniacal ammonium carbonate liquor having an ammonia content of from 205 to 330 gl-1 and a carbon dioxide content of from 160 to 300 gl-1.
20. A process according to claim 19, wherein the ammonia content is about 285 gl-1 and the carbon dioxide content is about 230 gl-1, and the reaction takes place in a series of mixer settler strip cells at a strip cell temperature of between 35° and 55°C for a period of between 30 seconds and 30 minutes in each cell.
21. A process according to claim 16, wherein the cobalt III tertrammine rich ammoniacal liquor is contacted with the organic reagent in a series of extract mixer settler units in an organic to aqueous ratio of from about 0.2:1 to 5:1.
22. A process according to claim 21, wherein the cobalt III tertrammine rich ammoniacal liquor is contacted with the organic reagent in an organic to aqueous ratio of from 1:1 to 2:1, for a period of between 30 seconds and 30 minutes in each extract cell, at an extract cell temperature of between 35° and 60°C.
23. A process according to claim 2, wherein the ion exchange resin is a chelating ion exchange resin of the iminodiacetate type with a high affinity for calcium and magnesium in order to extract calcium and magnesium from the cobalt III tetrammine rich ammoniacal liquor.
24. A process according to Claim 1 or 2, wherein cobalt III is recovered form the cobalt III tetrammine rich ammoniacal liquor as an intermediate by distilling the ammoniacal liquor with steam and pumping the aqueous slurry to a thickener to recover the suspended cobaltic oxide hydroxide solids.
25. A process according to Claim 2, wherein cobalt III is recovered from the cobalt III
tetrammine rich ammoniacal liquor by treating the ammoniacal liquor exiting the ion exchange resin system in a reductive step by contacting the ammoniacal liquor with finely divided pure cobalt metal powder to reduce the cobalt III tetrammine to labile cobalt II ammine, in an inert atmosphere at a temperature from 25°C to 35°C, resulting in the precipitation of cobalt hydroxy carbonate solids.
28. A cobalt intermediate prepared by the process according to claim 1 or 2.
18. A process according to claim 17, wherein the organic reagent is a mixture of 2-hydroxy-5-t-nonyl acetophenoneoxime in aliphatic kerosene, modified by the addition of iso-tridecanol.
19. A process according to claim 18, wherein prior to extracting nickel from the cobalt tetrammine rich ammoniacal liquor, any residual nickel is removed from the organic reagent by contacting the organic reagent with a high strength ammoniacal ammonium carbonate liquor having an ammonia content of from 205 to 330 gl-1 and a carbon dioxide content of from 160 to 300 gl-1.
20. A process according to claim 19, wherein the ammonia content is about 285 gl-1 and the carbon dioxide content is about 230 gl-1, and the reaction takes place in a series of mixer settler strip cells at a strip cell temperature of between 35° and 55°C for a period of between 30 seconds and 30 minutes in each cell.
21. A process according to claim 16, wherein the cobalt III tertrammine rich ammoniacal liquor is contacted with the organic reagent in a series of extract mixer settler units in an organic to aqueous ratio of from about 0.2:1 to 5:1.
22. A process according to claim 21, wherein the cobalt III tertrammine rich ammoniacal liquor is contacted with the organic reagent in an organic to aqueous ratio of from 1:1 to 2:1, for a period of between 30 seconds and 30 minutes in each extract cell, at an extract cell temperature of between 35° and 60°C.
23. A process according to claim 2, wherein the ion exchange resin is a chelating ion exchange resin of the iminodiacetate type with a high affinity for calcium and magnesium in order to extract calcium and magnesium from the cobalt III tetrammine rich ammoniacal liquor.
24. A process according to Claim 1 or 2, wherein cobalt III is recovered form the cobalt III tetrammine rich ammoniacal liquor as an intermediate by distilling the ammoniacal liquor with steam and pumping the aqueous slurry to a thickener to recover the suspended cobaltic oxide hydroxide solids.
25. A process according to Claim 2, wherein cobalt III is recovered from the cobalt III
tetrammine rich ammoniacal liquor by treating the ammoniacal liquor exiting the ion exchange resin system in a reductive step by contacting the ammoniacal liquor with finely divided pure cobalt metal powder to reduce the cobalt III tetrammine to labile cobalt II ammine, in an inert atmosphere at a temperature from 25°C to 35°C, resulting in the precipitation of cobalt hydroxy carbonate solids.
28. A cobalt intermediate prepared by the process according to claim 1 or 2.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AUPM209293 | 1993-10-29 | ||
| AUPM2092 | 1993-10-29 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2134490A1 CA2134490A1 (en) | 1995-04-30 |
| CA2134490C true CA2134490C (en) | 2000-05-23 |
Family
ID=3777315
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002134490A Expired - Fee Related CA2134490C (en) | 1993-10-29 | 1994-10-27 | Process for the preparation of a high purity cobalt intermediate |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US5605668A (en) |
| EP (1) | EP0651062B1 (en) |
| AT (1) | ATE175245T1 (en) |
| CA (1) | CA2134490C (en) |
| DE (1) | DE69415633T2 (en) |
| ES (1) | ES2126071T3 (en) |
| ZA (1) | ZA948497B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5650057A (en) * | 1993-07-29 | 1997-07-22 | Cominco Engineering Services Ltd. | Chloride assisted hydrometallurgical extraction of metal |
| AU694821B2 (en) * | 1995-01-09 | 1998-07-30 | Lionore Australia (Avalon) Pty Ltd | The recovery of nickel and cobalt from lateritic ores |
| CN1101475C (en) * | 1996-01-16 | 2003-02-12 | 中国科学院化工冶金研究所 | Method for recovering cobalt |
| US6231823B1 (en) | 2000-03-27 | 2001-05-15 | Dynatec Corporation | Solvent extraction process for the separation of cobalt from nickel in aqueous sulphate-containing solutions |
| US7096498B2 (en) | 2002-03-08 | 2006-08-22 | Cipher Trust, Inc. | Systems and methods for message threat management |
| AU2003901727A0 (en) * | 2003-04-11 | 2003-05-01 | Qni Technology Pty Ltd | Reductive ammoniacal leaching of nickel and cobalt bearing materials |
| RU2540257C1 (en) * | 2013-10-18 | 2015-02-10 | Федеральное Государственное Бюджетное Учреждение Науки Институт Химии И Химической Технологии Сибирского Отделения Российской Академии Наук (Иххт Со Ран) | Cobalt and nickel separation method |
| CN109200978B (en) | 2018-03-01 | 2023-06-06 | 中国石油大学(北京) | Method and system for treating waste catalyst of chloroaluminate ionic liquid and alkaline wastewater |
Family Cites Families (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3767762A (en) * | 1972-01-04 | 1973-10-23 | Sherritt Gordon Mines Ltd | Recovery and separation of nickel and cobalt from reduced laterite nickel ore |
| US3907966A (en) * | 1972-06-28 | 1975-09-23 | Kennecott Copper Corp | Nickel extraction and stripping using oximes and ammoniacal carbonate solutions |
| US3981968A (en) * | 1973-10-19 | 1976-09-21 | Freeport Minerals Company | Solvent extraction of nickel from ammoniacal solutions |
| SE387962B (en) * | 1975-01-28 | 1976-09-20 | Jungner Ab Nife | WAY TO SELECTIVELY RECYCLE CADMIUM FROM CADMIUM-CONTAINING WASTE |
| US4145397A (en) * | 1976-08-06 | 1979-03-20 | Marubeni Corporation | Process for recovering molybdenum, vanadium, cobalt and nickel from roasted products of used catalysts from hydrotreatment desulfurization of petroleum |
| US4153522A (en) * | 1977-06-09 | 1979-05-08 | The Anaconda Company | Sulfate precipitation during oxidative ammonium leach of Cu, Ni, Zn sulfide ores |
| US4348367A (en) * | 1980-08-28 | 1982-09-07 | American Cyanamid Company | Selective removal of cobalt(II) from aqueous solutions with phosphinic extractants |
| US4432953A (en) * | 1982-09-24 | 1984-02-21 | Chevron Research Company | Leaching cobalt from spent hydroprocessing catalysts with sulfur dioxide |
| US4515757A (en) * | 1982-09-24 | 1985-05-07 | Chevron Research Company | Stripping a solution containing molybdenum, tungsten and/or vanadium values |
| US4563213A (en) * | 1982-09-24 | 1986-01-07 | Chevron Research Company | Extraction and stripping cobalt values |
| US4434141A (en) * | 1982-09-24 | 1984-02-28 | Chevron Research Company | Recovery of cobalt, molybdenum, nickel and vanadium from an aqueous ammonia and ammonium salt solution by coextracting molybdenum and vanadium and sequential extraction of nickel and cobalt |
| US4514369A (en) * | 1982-09-24 | 1985-04-30 | Chevron Research Company | Recovery of cobalt, molybdenum, nickel, tungsten and vanadium from an aqueous ammonia and ammonium salt solution by coextracting molybdenum, tungsten and vanadium and sequential extraction of nickel and cobalt |
| US4600435A (en) * | 1984-08-24 | 1986-07-15 | Amax Inc. | Solvent extraction of cobalt (II) from sulfate solutions with cobalt extractants |
| CA1227339A (en) * | 1984-09-17 | 1987-09-29 | Juraj Babjak | Process for metal recovery by solvent extraction from caso.sub.4 containing sulfate solutions |
| US4900522A (en) * | 1986-07-22 | 1990-02-13 | Amax Inc. | Separation of nickel and cobalt from sulfate solutions by solvent extraction |
| ID827B (en) * | 1987-05-20 | 1996-07-25 | Meq Nickel Pty Ltd | SEPARATION AND REQUIREMENT OF NICKEL AND KOBAL BACK IN AMONIAC SYSTEMS |
| US4956154A (en) * | 1988-03-09 | 1990-09-11 | Unc Reclamation | Selective removal of chromium, nickel, cobalt, copper and lead cations from aqueous effluent solutions |
| US5010049A (en) * | 1989-03-24 | 1991-04-23 | The Regents Of The University Of Michigan | Modified molybdenum sulfide hydrodesulfurization/hydrodenitrogenation catalysts |
| US5228903A (en) * | 1990-04-18 | 1993-07-20 | The Curators Of The University Of Missouri Of Columbia | Method for stripping metals in solvent extraction |
-
1994
- 1994-10-27 CA CA002134490A patent/CA2134490C/en not_active Expired - Fee Related
- 1994-10-27 US US08/329,848 patent/US5605668A/en not_active Expired - Lifetime
- 1994-10-28 EP EP94307953A patent/EP0651062B1/en not_active Expired - Lifetime
- 1994-10-28 DE DE69415633T patent/DE69415633T2/en not_active Expired - Lifetime
- 1994-10-28 AT AT94307953T patent/ATE175245T1/en not_active IP Right Cessation
- 1994-10-28 ZA ZA948497A patent/ZA948497B/en unknown
- 1994-10-28 ES ES94307953T patent/ES2126071T3/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| ATE175245T1 (en) | 1999-01-15 |
| EP0651062A1 (en) | 1995-05-03 |
| DE69415633D1 (en) | 1999-02-11 |
| DE69415633T2 (en) | 1999-05-20 |
| ZA948497B (en) | 1995-06-20 |
| ES2126071T3 (en) | 1999-03-16 |
| CA2134490A1 (en) | 1995-04-30 |
| EP0651062B1 (en) | 1998-12-30 |
| US5605668A (en) | 1997-02-25 |
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| MKLA | Lapsed |